DE2759233A1 - WATER-BASED HYDRAULIC LIQUIDS - Google Patents

Description

- 2 - ϋ.Z. £ 970/00899

Water-based hydraulic fluids

The present invention relates to hydraulic fluids and water-based cutting fluids.

In the technology of hydraulic power transmission, mechanical power in the form of pressure is generated by a hydraulic pump Communicated fluid, which is referred to as "hydraulic fluid". The force in the form of pressure is applied to the desired Place converted back into mechanical movement by tapping a line carrying the hydraulic fluid, and with the help of a device called "hydraulic motor". The hydraulic fluid is used as a pressure and volume transferring Medium used. Any non-compressible liquid is suitable for this. Water is the oldest hydraulic fluid and is sometimes still used on its own today. So far, however, the focus has been on the development of hydraulic fluids on the mineral oils; accordingly, much of the hydraulic fluid devices are special designed and built for the use of such mineral oils. In comparison to water as hydraulic fluid, a mineral oil works wear-reducing and inhibits the formation of rust on iron parts of the devices working with hydraulic fluids (hydraulic pumps, motors, etc.). Mineral oils have the advantage over water as a hydraulic fluid that they are normally an essential have higher viscosity and thus contribute to reducing leakage losses in the mechanical devices. About that In addition, the development in the field of mineral oil additives has advanced so far that viscosity, anti-foam properties and the corrosion-inhibiting effect is further improved by such additives can be.

Over the past 25 years, various mineral oil hydraulic fluid substitutes have been developed to be one of the Main disadvantages of mineral oils, to eliminate their flammability.

809828/0764 ³ "

- 3 - O, Z. 297O / OO899

The increased costs for mineral oils and the problem of the environmentally friendly disposal of contaminated or used hydraulic fluids based on mineral oils, which has recently become more and more important, have led to recent interest in the use of hydraulic fluids with a water content of up to 99 % and above is.

Cutting fluids with so-called "soluble oils" are also available has already been considered for use as hydraulic fluids. Such liquids contain mineral oil and emulsifiers and various additives to increase corrosion resistance and improve wear-reducing properties and anti-foam properties. Such fluids are not generally for use in ordinary ones as hydraulic fluids industrial devices specially designed to operate with mineral oil-based hydraulic fluids were suitable because they do not have a sufficient wear-reducing effect in the pumps and valves of these devices. They have but found application in specially designed, complex, extensive facilities that because of their size and the resulting low flexibility are unsuitable for most industrial plants. The use of hydraulic fluids this type has therefore remained very limited; it is largely limited to extensive systems in which it Flexibility and size are not important, e.g. in steel works.

U.S. Patent 3,249,53S describes the manufacture of a aqueous lubricant concentrate and lubricant consisting essentially of molybdenum disulfide and a water-soluble Viscosity increasing agents such as polyvinyl alcohol and emulsifiable mineral oil exist. From U.S. Patent 3,970,569 is known to produce aqueous lubricants containing a water-soluble mixed ester, the transesterification of a Polyoxyethylene glycol and a triglyceride was obtained.

809828/0764

- '4 - uZ 2970/00899

From U.S. Patent 3,953,653 is known to be a mixture as an additive to use from a phosphate ester and a sulfur compound in a cutting fluid containing water in order to do so To achieve extreme pressure, wear-reducing and anti-corrosion properties. Such additives are used along with a suitable one Carriers such as mineral oil, vegetable oils, esters of aliphatic acids, etc. are used. It is the sulfur compounds are not sulfur-molybdenum compounds, but rather derivatives of 2-mercaptobenzothiazole. The phosphate esters of the invention however, are similar to the phosphate esters mentioned in this patent. These are alkylene oxide derivatives an alkyl, aryl or arylalkyl phosphate, which is in the form of the free acid or in the form of the neutralized phosphate ester neutralized with a metal hydroxide or carbonate, ammonia or an amine, can be used. The usage this phosphate ester in water-based cutting fluids is proposed in ASLE Transactions 7, (see 398-405) on page Ί05.

There is no reference in any of the above-mentioned references insists that a water-based hydraulic or cutting fluid is obtained by (1) a water-soluble polyoxyethylene Esters of an aliphatic acid or an aliphatic alcohol with (2) a sulfur-molybdenum or sulfur-antimony compound mixes, the liquid additionally (3) an aliphatic, aromatic or alkyl aromatic phosphate ester may contain.

According to the present invention, a water-based hydraulic or cutting fluid is obtained by adding water, a sulfur-molybdenum or sulfur-antimony compound and a water-soluble Cg-C ,, - ester of an oxethylated aliphatic alcohol and an oxethylated aliphatic acid mixes with one another, alcohol or acid or both alcohol and acid are oxethylated.

809828 / 07S4

- 5 - O.Z. 297O / OO899

It is also possible to use a hydraulic or cutting fluid Produce water-based by adding water and (1) a phosphate ester made by esterifying 1 mole of phosphorus pentoxide with 2 to M, 5 moles of a nonionic surfactant, the by condensation of at least 1 mole of ethylene oxide with 1 mole of a compound having at least 6 carbon atoms and one reactive Hydrogen atom obtained v / urde, with (2) a water soluble Esters prepared by reacting an oxethylated alcohol or an oxethylated aliphatic acid with 8 up to 36 carbon atoms, and (3) a Schvrefel molybdenum or Sulfur-antimony compound mixed. Stable concentrates with these ingredients can be used both with and without water produce. If desired, the mixtures can also be mixed with a thickener of the polyglycol or polyacrylate type or another known thickening agent such as sorbitol, polyvinylpyrrolidone and polyvinyl alcohol. For improvement Corrosion inhibitors can also be added to the corrosion-inhibiting properties.

Molybdenum oxysulfide dithiocarbamate and oxymolybdenum phosphorodithioate are suitable as molybdenum compounds. As antimony compounds those with a similar structure are suitable.

The concentrates according to the invention, when mixed with a large amount of water, can be used as flame-retardant hydraulic fluids with excellent lubricity and anti-wear properties or as cutting fluids for cooling and lubrication of those in frictional contact with each other Use surfaces, e.g. when turning, planing, peeling and grinding metals. The hydraulic and cutting fluids of the invention are the known liquids with a mineral oil content or based on environmental friendliness superior to a glycol / water mixture.

The present invention describes hydraulic and cutting fluids as well as lubricant concentrates which, when mixed with water

809828 / 07S4 - 6 -

- β - O. - :. .'970 / 00899

thins, hydraulic and cutting fluids result. The invention Mixtures have both the lubricity and the wear-inhibiting properties that a hydraulic or Must have cutting fluid. The use of a phosphate ester with a combination of water, a water-soluble ester of an oxethylated aliphatic acid or an oxethylated aliphatic alcohol and a sulphurous molybdenum or antimony compound results in hydraulic fluids, that exhibit synergistic improvements in their performance. Compared to hydraulic fluids, which are only water-soluble ethoxylated aliphatic esters and containing sulfur-containing molybdenum or antimony compounds can be achieved with hydraulic fluids, which also contain a phosphate ester, in practical tests a lower weight loss as a result from wear and tear. As is customary in this field, the mixtures according to the invention can also contain anti-corrosion agents, antifoam agents, Add agents to increase viscosity and metal deactivators (chelating agents).

Water-soluble esters of ethoxylated aliphatic monohydric or polyhydric alcohols having 8 to 38 carbon atoms with aliphatic acids and aliphatic dimer acids are preferably used as the wear-reducing component of the lubricant concentrates and hydraulic and cutting fluids according to the invention. Such ethoxylated esters have an HLB value (HLB = hydrophilic- lipophilic balance) of 10 to 20. The most advantageous adducts have an HLB value of 13 to 18.

Are suitable ethoxylated aliphatic acids having from about 5 to 20 moles of ethylene oxide per mole of acid, for example, ethoxylated oleic acid, ethoxylated stearic acid and ethoxylated palmitic acid. Suitable ethoxylated dimer acids are dimer oleic acid and dimer stearic acid. The aliphatic acids can be straight or branched chain and contain from about 8 to about 36 carbon atoms. For example, azelaic, sebacic, dodecanedicarbon,

- 7 809828/0764

- 7 - O.Z. 2970/00899

Caprylic, capric, lauric, oleic, stearic and palmitic acids. For the preparation of the water-soluble esters according to the invention in particular suitable acids are aliphatic (especially saturated and straight-chain) mono- and dicarboxylic acids with about 8 to 18 carbon atoms.

The dimer acids used in the preparation of the water-soluble esters are obtained by polymerizing unsaturated fatty acids having 16 to 26 carbon atoms or their ester derivatives. The polymerization of fatty acids to dimeric fatty acids is described in detail in the relevant literature and therefore does not need to be discussed in more detail here. Dimer acids preferably used for the production of the polyesters are those with 36 carbon atoms, for example the dimer of linoleic acid or eleostearic acid. Dimer acids with 32 to 5 ^ carbon atoms can also be used. The dimeric acids do not need to be used in pure form, but can be used in a mixture with unpolymerized acid or with more highly polymerized acid, for example with trimeric and tetrameric acids, but the proportion of dimeric acid in the mixture is more than 50 % .

The esters of ethoxylated aliphatic acids and dimeric acids used in the hydraulic and cutting fluids according to the invention are used, are obtained by reaction with the ethoxylated mono- or polyhydric alcohols.

Suitable monohydric alcohols are, for example, n-octyl, n-decyl, n-dodecyl- (lauryl-), n-tetradecyl- (myristyl-), n-hexadecyl- (cetyl-) and n-octadecyl alcohol. Suitable polyhydric alcohols are e.g. ethylene glycol, diethylene glycol, polyethylene glycol, sucrose, butanediol, butenediol, butynediol, hexanediol and polyvinyl alcohol. Glycerin, sorbitol, pentaerythritol, trimethylolethane and trimethylolpropane are particularly suitable polyhydric alcohols.

- 8 809828 / 07B4

- 8 - O.Z. 297O / OO899

Suitable monohydric aliphatic alcohols are generally those having straight chains and 8 to 18 carbon atoms. The alcohols are ethoxylated in such a way that about 5 to 20 moles of ethylene oxide are added according to conventional ethoxylation processes known to those skilled in the art. These processes are carried out under pressure in the presence of alkaline catalysts. The monohydric aliphatic alcohols preferred for the preparation of the ethoxylated aliphatic alcohols according to the invention are the straight-chain primary alcohols with a chain length of C ₁₂ to C ₁ C, which are available from Shell Chemical Company under the trademarks "Neodol 25-3" and "Neodol 25-" 7 "are distributed.

Typical examples of water-soluble polyoxyethylene esters with about 5 to 20 moles of oxide per mole are the polyoxyethylene derivatives of the following esters: sorbitan monooleate, sorbitan trioleate, sorbitan monostearate, Sorbitan tristearate, sorbitan monopalmitate, sorbitan monoisostearate and sorbitan monolaurate.

The sulfur-containing oxymolybdenum or oxyantimony organophosphorodithioate additives according to the invention correspond to the formula

O _n / S

J 2

in which M is molybdenum or antimony and R is an organic radical from the group consisting of C _{1 -C 20} -alkyl, aryl and alkylaryl and mixtures thereof.

Examples of suitable molybdenum and antimony compounds are molybdenum or antimony oxysulfide dithiocarbamate and sulfur-containing ones Oxyantimony or oxymolybdenum organophosphorodithioate in which the organic radical is alkyl, aryl or arylalkyl, where the

809828/0764 " ⁹ "

- 9 - O.Z. 297C / OCb99

Alkyl radical has a chain length of 3 to 20 carbon atoms.

The mixtures according to the invention contain a phosphate ester of the formula

Il

RO - (AO) _n - P-OX

OX
or

It

RO - (AO) _n - P - (AO) _n - OR OX

or a mixture of these phosphate esters, in which ÄO ethylene oxide, R is a linear or branched chain alkyl group with about 6 to about 30, preferably about 8 to about 20 carbon atoms, or an arylalkyl group with about 6 to about 30, preferably about b to about 18 carbon atoms in the alkyl group, X ammonia, an amine or an alkali metal, an alkaline earth metal or mixtures thereof and η is a number from 1 to 50. X can E.g. metals such as lithium, sodium, potassium, rubidium, cesium, calcium, strontium and barium mean.

The phosphate esters used in the mixtures according to the invention are discussed in more detail in U.S. Patents 3,004,056 and 3,004,057.

In general, the phosphate esters to be used according to the invention are obtained by esterifying 1 mol of P ₂ ° 5 ^m * ^{fc 2 to} ** » ^ mol of a nonionic surfactant which is a condensation product of at least 1 mol of ethylene oxide with 1 mol of a compound having at least 6 carbon atoms and a reactive water

- IC 809828/0764

- 10 - O.Z, 2970/00899

is hydrogen atom. Such nonionic surfactants are known and are prepared by adding a polyglycol ether having a suitable number of alkenoxy groups or a 1,2-alkylene oxide or substituted alkylene oxide, such as 3. substituted propylene, butylene or, preferably, ethylene oxide, with an organic Condensed compound with at least 6 carbon atoms and one reactive hydrogen atom. Connections that contain a reactive hydrogen atom are e.g. alcohols, phenols, thiols, primary and secondary amines, and carbon and sulfonic acids and their amides. The amount of alkylene oxide or equivalent that condenses with the reactive chain depends primarily on the compound with which it is condensed. In general, a condensation product is obtained with a content of 20 to 85 percent by weight of condensed-in alkylene oxide units. The optimal amount of alkylene oxide or equivalent, however, depends on the desired HLB value.

The nonionic surfactants used are preferably derivatives of alkylated and polyalkylated phenols, multi-branched ones primary aliphatic alcohols with the molecular structure of an alcohol, which according to the oxo process from a polyolefin with at least 7 carbon atoms, and straight-chain aliphatic alcohols with at least 10 carbon atoms. Examples for suitable non-ionic surfactants, those with phosphorus pentoxide as additives to the hydraulic fluids according to the invention Phosphate esters used can be implemented are listed below. In this list, "AO" means ethylene oxide and the preceding number is the number of moles associated with 1 mole of the specified reactive hydrogen-containing compound implemented.

- 11 -

809828/0764

O.Z. 297O / OO899

Nonylphenol + 9 to 11 AO nonylphenol + 2 AO dinonylphenol + 7 AO dodecylphenol + 18 AO Castor oil + 20 AO tall oil + 18 AO

Oleyl alcohol + HÄO oleyl alcohol + 20 ÄO lauryl alcohol + 4 ÄO Lauryl alcohol + 15 ÄO hexadecyl alcohol + 12 ÄO hexadecyl alcohol + 20 ÄO Octadecyl alcohol + 20 ÄO oxotridecyl alcohol:

(from tetrapropylene) + 7 ÄO (from tetrapropylene) + 10 ÄO (from tetrapropylene) + 15 ÄO Dodecyl mercaptan + 9 AO soybean oil amine + 10 AO Rosin amine + 32 AO coconut fatty acid amine + 7 AO cocoa fatty acid + 10 AO Dodecylbenzenesulfonaraid + 10 EO decylsulfonamide + 6 EO oleic acid + 5 AO

Polypropylene glycol (30 oxypropylene units) + 10 AO

It is known that the phosphate esters according to the invention, as already mentioned, can improve the wear-reducing and extreme pressure properties of a lubricant mixture; however, it has been found that synergistic improvement in these properties is obtained by using the phosphate esters with the water-soluble oxethylated esters of the invention and the sulfur-containing molybdenum or antimony compound according to the invention combined.

809828/0764

- 12 -

- 12 - O.Z, 297O / CO899

It is believed that the increase in lubricity and anti-wear Properties on the arylalkyl or alkylpolyethoxyethylene moieties is due, while the phosphorus contained in the compound to improve the wear-resistant and extreme pressure properties of the lubricant.

The hydraulic and cutting fluids according to the invention generally consist of 60 to 99 % water and 40 to 1 % additives. These additives can be concentrated mixtures of the water-soluble esters of ethoxylated aliphatic acids and mono- or polyhydric aliphatic alcohols, molybdenum or antimony compounds and a phosphate ester and can also contain polymeric thickeners, antifoams, corrosion inhibitors and metal deactivators or chelating agents. The liquids according to the invention preferably consist of about 75 to 99 % water and about 25 to 1 % of additional concentrate. The liquids can easily be diluted with distilled or demineralized water at room temperature; however, tap water can also be used for this without having to fear that the properties of the liquids will be impaired.

Stable concentrates of the invention can also be used Manufacture hydraulic and cutting fluids. They can either be completely anhydrous, as indicated below, or one Any amount of water, preferably up to 75 percent by weight water, so that they become more fluid and stick to the Mix the place of use with water more easily. These concentrates are generally used in a ratio of 1:99 to 10:90 with water diluted.

Such concentrates are e.g. the following:

- 13 -

809828/0764

O.Z. 297C / OC899

Table 1 component

Polyoxyethylene (20) sorbitan monostearate alkyl phosphate ester according to example 5

Sulfur-containing oxymolybdenum or Oxyantimony organophosphorodithioate (pesticide content 40 *)

Sodium 2-mercaptobenzothiazole

Isopropylaminoethanol or morpholine

water

Weight percent

20 16 38 30 19 9

5 4 8 6 4 2

15 12 31 26 15 8

20 16 8 6 4 2

40 32 15 12 8 4

- 20 - 20 50 75

The ratio of phosphate ester to sulfur-containing molybdenum or antimony compound is generally about 0.1: 1 to about 2: 1 based on the weight of the sulfur in the sulfur-containing molybdenum or antimony compound. The ratio of water-soluble ester of ethoxylated aliphatic acid or ethoxylated aliphatic alcohol to sulfur-containing molybdenum or antimony compound is about 0.5: 1 to about 2: 1, based on the weight of the sulfur in the sulfur-containing molybdenum or antimony compound. The ratio of phosphate ester to sulfur-containing molybdenum or antimony compound is preferably 0.5: 1 to 1: 1 and the ratio of water-soluble ester of the ethoxylated aliphatic acid or the ethoxylated aliphatic alcohol to sulfur-containing molybdenum or antimony compound about 1: 1 to about 1.5: 1.

In the hydraulic or cutting fluids according to the invention, the concentration of the sulfur-containing molybdenum or antimony compound, based on water, is generally from about 0.05 to about 3 percent by weight, the concentration of the phosphate ester, based on water, about 0.05 to about 1 percent by weight and the Concentration of the water-soluble ester of the ethoxylated ali-

- 14 -

809828/0764

- 14 - O.Z. 297O / OC899

phatic acid or ethoxylated aliphatic alcohol, based on water, about 0.1 to about 5 percent by weight. Preferably these concentrations are 0.075 to 0.5, 0.25 to 0.5 and 1 to 2 percent by weight, respectively.

In the case of thickeners, metal deactivators and anti-corrosion agents that can be added to either the concentrate or the hydraulic or can add cutting fluids of the invention, they are the following:

Any alkali metal nitriles, nitrates and benzoates can be used as liquid and vapor phase corrosion inhibitors. Certain Amines are also suitable. The funds can be used alone or in a mixture. Preferred alkali nitrates and -benzoates are e.g. sodium nitrate, potassium nitrate, calcium nitrate, barium nitrate, lithium nitrate, strontium nitrate, sodium benzoate, Potassium benzoate, calcium benzoate, barium benzoate, lithium benzoate and strontium benzoate.

Corrosion protection agents of the amine type are e.g. morpholine, N-methylmorpholine, N-ethylmorpholine, ethylenediamine, dimethylaminopropylamine, Ν, Ν-dimethylethanolamine, oC and 7 "picoline, Piperazine and isopropylaminoethanol.

Particularly preferred vapor phase corrosion inhibitors are morpholine and isopropylaminoethanol. You bet about 0.05 to about 2 percent by weight of anti-corrosion agent of this type, based on the total weight of the hydraulic or hydraulic system according to the invention Snow fluid. These amines are preferably used in an amount of about 0.5 to about 2 percent by weight.

The metal deactivators are primarily used for chelation used by copper and copper alloys. These materials are well known to those skilled in the art and can be selected from the large Classes of substances suitable for this purpose are selected

- 15 809828/0784

- 15 - O.Z. 297O / CO899

will; this subheading includes the various triazoles and thiazoles as well as the amine derivatives of salicylidenes. Examples of these metal deactivators are benzotriazole, tolytriazole, 2-mercaptobenzothiazole, Sodium 2-mercaptobenzothiazole and N, N'-disalicylidene-1,2-propanediamine.

Other anti-corrosion agents can also be used. In addition to the amines, alkali nitrates, benzoates and nitriles mentioned above, alkoxylated fatty acids are also used as corrosion protection agents suitable.

In view of the expected operating conditions, it can be useful to add a thickening agent to the hydraulic and cutting fluids according to the invention. For example, a thickener of the polyglycol type can be used. Such thickeners are well known and are preferably used in the present case because they have particular advantages with regard to the Newtonian viscosity properties under changing shear conditions. These thickeners are polyoxalkylene polyols made by reacting an alkylene oxide with a straight or branched chain polyhydric alcohol. These polyols contain ethylene oxide and propylene oxide units in a molar ratio between about 100: 0 and about 70:30. They are commercially available under the trademark "Ucon 75H 90,000" (Union Carbide and Carbon Chemical Corporation); according to the specification of this product has a pour point of 4 ° C, a flash point of 252 ° C, a specific gravity of 1.095 at 20 ⁰ C and a viscosity of about 90,000 SUS (Saybolt Universal Seconds) at 38 ° C. In general, about 2 to about 20 % , preferably about 5 to about 15% polyglycol thickener, based on the total weight of the hydraulic or cutting fluid according to the invention, is used.

You can increase the viscosity of the hydraulic system according to the invention and cutting fluids also use other additives, e.g. polyvinyl alcohol, polymers of acrylic and methacrylic acid, Polyvinylpyrrolidone-polyvinylether-maleic anhydride copolymer

809828/0764

- 16 -

- 16 - O.Z. 297ü / Cü899

sat and sorbitol. These substances are well known to those skilled in the art and are used in varying amounts depending on the viscosity desired and the effectiveness of the thickener in question. In general, such thickeners are obtained in the fluids of this invention by the addition of etifa 3 to about 15% and a viscosity of about 100 SUS at 38 ⁰ C. The use of these thickening agents in the inventive hydraulic fluids can probably wear due to cavitation and internal and To a large extent prevent external leakage losses while pumping the hydraulic fluids.

The phosphate ester and the esters of ethoxylated aliphatic acids and monohydric and polyhydric alcohols as described above are water-soluble, in the sense that no special procedure is required to get these substances into water to disperse and keep in suspension for a long time. In contrast, the sulfur-containing molybdenum or antimony compounds insoluble in water and must therefore be emulsified before use, e.g. with the help of anionic or nonionic surfactants. Suitable surfactants of this type are sodium dodecylbenzenesulfonate, polyoxyethylated fatty alcohols and fatty acids and polyoxyethylated fatty acids Alkyl phenols.

A typical recipe for emulsifying those of the invention sulfur-containing molybdenum or antimony compound (sulfur-containing oxymolybdenum or oxyantimony organophosphorodithioate) the following:

Emulsifier weight percent

Sodium dodecylbenzenesulfonate 70

Ethylene glycol monobutyl ether 23

Butyl alcohol 7

TÜO "

- 17 809828/0764

O.Z. 297Ο / ΟΟ899

Emulsifiable concentrate

Molybdenum or antimony compound containing sulfur

Emulsifier Weight percent

60
100

A typical hydraulic or cutting fluid according to the invention with a high water content has the following composition, for example:

Table 2 Composition of a typical hydraulic or cutting fluid component

Water (distilled or demineralized) Polymeric thickener
Water-soluble ethoxylated ester

Molybdenum or antimony compound (pesticide content MO %)

Water soluble alkyl phosphate ester

Metal deactivators

Anti-corrosive agents

Weight percent

95 0

0.1 0.1 0.5

70 15 10

1-5

1.0

0.5 1.0

The hydraulic and cutting fluids according to the invention are, if they correspond to the above formulation, transparent fluids with a viscosity of up to 400 SUS at 38 ^° C., which are stable for a long time when stored at room temperature. In addition, they are free of oil and therefore does not support combustion, in contrast to the conventional flame-resistant fluids based on glycol and water, or mineral oils. The hydraulic and cutting fluids according to the invention are environmentally friendly compared to conventional fluids based on mineral oil. Since they are great

- 18 -

809828/0764

- 18 - O.Z, 297O / CO899

Partly consisting of synthetic substances that are not derived from petroleum, their production is relatively independent of Oil shortages and is not significantly influenced by the economic effects of such shortages.

The hydraulic fluids according to the invention are for various purposes Suitable for applications where a hydraulic pressure of 14 to 140 kg / cm is required; they have all the necessary for it Properties such as lubricity, viscosity and corrosion protection. They are suitable for use in various Hydraulic systems, especially in systems that work with vane or piston pumps. Such pumps are used there where hydraulic pressure for forming, clamping and pressing metals, for operating devices such as doors and elevators, to close the molds in pressure and injection molding machines, etc. is required.

The Vickers vane pump test is used to test the hydraulic fluids according to the invention. The device used in this test is a hydraulic system that operates as follows. Hydraulic fluid is drawn in from a closed sump by a vane pump of the Vickers V-IO ¹ JE type. The pump is driven directly by a 25 HP electric motor with a speed of 17 ^ 0 rpm. The liquid leaves the pump through a pressure control valve, then passes through a calibrated Venturi tube (for flow measurement) and is returned to the sump. The liquid is cooled in a heat exchanger operated with cold water. The supply of heat is not required because the temperature of the liquid increases as a result of the frictional heat generated by the action of the pump on the liquid, excess heat is removed by the fact that the liquid is passed through before it is returned to the sump conducts the heat exchanger. The Vickers V 104E wing purape has a cylindrical housing (pump body) in which the so-called "pump cartridge" is located. This exists

- 19 809828/0764

- 19 - O.Z, 297Ο / ΟΟ899

consisting of a front and rear round brozene box, a rotor, a cam ring and rectangular blades. Bushings and cam ring rest on the pump body, and the rotor is connected to a shaft which is set in rotation by an electric motor will. A number of detachable vanes are arranged in slots in the circumference of the rotor. The cam ring also engages around the rotor its wings is surrounded by the cam ring and the bushings. The inner surface of the cam ring has a cam shape. By the rotary motion of the rotor results in a displacement of each cavity, the two adjacent ones through the rotor, the cam ring Wings and the cans is formed. The pump body is provided with openings through which liquid during rotation enters and exits the cavity.

The test method mentioned prescribes that the system is filled with 18.9 l of the liquid to be tested and at temperatures

from 38 to 57 ° C and a pump delivery pressure from 52.7 to

70.3 kg / cm operates. The wear values were determined by weighing the ring and the wings of the "pump cartridge ^11" before and after the test. At the end of the test, the pump was disassembled for weighing and the whole system was checked for signs of deposits, formation of oxidation products, corrosion etc. visually checked.

The following examples illustrate the invention and show the surprising results that can be obtained with the inventive Liquids achieved. The parts and percentages given in the examples relate, unless otherwise stated is on weight.

Example 1 (comparative example

A comparative water-based hydraulic fluid, which is the best in the art, was prepared by mixing 10 % of a water-soluble polyoxyethylene ester of sorbitan monostearate (20 moles of ethylene oxide per

809828/0764 - ²⁰ -

- 20 - O.Z. 29/0/00899

Mol Ester), sold under the trademark "EMSORB 6905" by Emery Industries, containing 12 % of a polyglycol thickener sold under the trademark "PLURACOL V-IO" by BASF Wyandotte Corporation. 1% of morpholine together with 1.8 % of the triethonalaminalses of 2-mercaptobenzothiazole were added as a vapor phase corrosion protection agent. The remainder of the liquid was demineralized water. The liquid was clear and had a viscosity of 140 - 15O SUS at 38 ⁰ C. The test according to the method described above (20 hours at a pressure of 52.7 kg / cm, a temperature of 38 ⁰ C and a speed of 1200 Rpm) resulted in a total weight loss of 848 mg.

Example 2

To produce a water-based hydraulic fluid according to the invention, "10% of a water-soluble polyoxyethylene ester of sorbitan monostearate, available under the trademark" EMSORB 6905 ", was mixed with 12 % of a polyglycol thickener available under the trademark" PLURACOL V-IO ". This mixture was with 1 % morpholine and 1.8 % of the triethanolamine salt of 2-mercaptobenzothiazole prepared as in Example 1 were added. Then 2 % of an emulsion (solids content 40%) of a sulfur-containing oxymolybdenum organophosphorodithioate, which is available from the RT Vanderbilt Company under the trademark " VANLUBE 723 ". The remaining part of the liquid was demineralized water. The liquid had ^{a viscosity of about 145 SUS at 38 °} C.; it was clear and amber. The test in the Vickers V-104c vane pump (20 hours at a pressure of 52.7 kg / cm, a temperature of 38 ⁰ C and a speed of 1200 rpm) gave a total Weig ht loss due to wear of 566 nig.

Example 3

To produce a hydraulic fluid, 10 % of a water-soluble polyoxyethylene ester of sorbitan monostearate was mixed,

809828/0764

- 21 -

- 21 - O.Z. 297Ü / CÜ899

available under the trademark ¹¹ EMSORB 6905 ", 2 % of an emulsion (pesticide content 40%) of a sulfur-containing oxymolybdenum organophosphorodithioate, available under the trademark" VANLUBE 723 ", and 0.5 % of a straight-chain alkyl phosphate ester, available under the trademark" ANTARA LB- 400 ", with 12 % of a polyglycol thickener sold under the trademark ¹¹ PLURACOL V-10". This mixture was mixed with 1 % morpholine and 1.8 * of the triethanolamine salt of 2-mereaptobenzothiazole as a liquid and vapor phase corrosion protection agent; the triethanolamine salt mentioned was prepared as described in Example 1. The hydraulic fluid was clear and amber-colored and had a viscosity of about 145 SUS at 38 ⁰ C. The test in the Vickers V-lOiJC-Plügelpumpe gave excellent results in terms of wear-reducing properties: kg 52.7 / cm pressure, 38 ⁰ C and 1200 rpm a surprisingly low weight loss of 117 mg was achieved. One second test with the same hydraulic fluid, but that

2 at a pressure of 70.3 kg / cm gave one

Weight loss of 120 mg. Example 4

The liquid according to Example 3 was diluted with demineralized water in a ratio of 4: 1. A clear liquid was obtained which had ^{a viscosity of about 85 SUS at 38 °} C. and which resulted in a weight loss of in the vane pump test described above (20 hours, 52.7 kg / cm ² , 38 ^{° C., 1200 rpm)} Scored 134 mg.

The results from Examples 1 to 4 are as follows Table 3 summarized. As can be seen from this, the result Hydraulic fluid according to Example 2 a considerable improvement over the result according to Comparative Example 1; after adding the phosphate ester to the hydraulic fluid according to example 2 one obtains, however, a disproportionately large reduction in the

- 22 -809828/0764

O.Z, 297C / CO899

weight loss (Example 3); this improvement is essentially retained if the liquid according to example 3 is diluted with an addition of 20% v / water (example 4).

Table 3

Results of the Vickers vane pump test of the hydraulic fluids according to the invention

Total weight loss

in mg

848 566 117

Hydraulic fluid according to the example

1 (comparative example)

Test conditions: Vickers V-104C vane pump, running time 20 hours, 52.7 kg / cm ² pressure at 38 ⁰ C, 1200 rpm.

Example 5

A water-based hydraulic fluid was prepared by mixing 5 % of an ester of polyoxyalkylated sorbitan monostearate (available under the trademark "EMSORB 6905"), 0.8 % of an emulsion (solids content 40%) of a sulfur-containing oxymolybdenum organophosphorodithioate (available under the trademark "MOLYVAN L ", RT Vanderbilt Company), which was emulsified in water with 1.2% of a mixture (1: 1) of the nonionic surfactants PLURAFAC D-25 and PLURAFAC A-24 (BASF Wyandotte Corporation), and 0.5 % of a Alkyl phosphate ester obtained by reacting 2 moles of phosphorus pentoxide with the surfactant condensation product of 1 mole of oleyl alcohol and 4 moles of ethylene oxide. In addition, 12 % of a polyglylcol Verdlclcun ^ sitiittels, available under the trademark ¹¹ PLURACOL V-IO ", and 1.8% of the triethanolamine salt of 2-mercaptobenzothiazole and 1% morpholine were used as a corrosion protection agent or metal deactivation agent.

- 23 -

809828/0764

- 23 - O.Z. 297O / C0899

medium (chelating agent) added. The remainder of the liquid was demineralized water. The hydraulic fluid obtained had ^{a viscosity of 125 SUS at 38 °} C. and was clear and amber in color.

The Vickers vane pump test (20 hours, 49.2 kg / cm ² , 1200 rpm, 38 ^° C.) resulted in a weight loss of 146 mg.

Example 6

A water-based hydraulic fluid was prepared by mixing 15 % of the ester of polyoxalkylated sorbitan monostearate available under the trademark "EMSORB 6905", 2 % of the emulsion mentioned in Example 5 (solids content MO%) of sulfur-containing oxymolybdenum organophosphorodithioate and 0.5 ί of the in Example 5 used phosphate ester. In addition, 8 % of a polyglycol thickener available under the trademark "PLURACOL V-10" and a mixture of 1.8 % of the triethanolamine salt of 2-mercaptobenzothiazole and 10 % morpholine were added as a corrosion protection and metal deactivator. The liquid had a viscosity of about 95 SUS at 38 ^° C. and was clear and amber in color. The Vickers vane pump test under the conditions given in Example 5 showed a weight loss of 184 mg.

Example 7

A water-based hydraulic fluid was prepared with a composition similar to that of Example 6, but using 3 % of the emulsion described in Example 5 (solids content 40%) of sulfur-containing oxymolybdenum organophosphorodithioate together with 1 % of the phosphate ester described in Example 5. In addition, 8 % of the polyglycol thickener available under the trademark “PLURACOL V-IO” and the mixture of corrosion inhibitor and metal deactivator described in Example 5 were used. One received

809828/0764

- 24 - O.Z, 297O / OO899

a clear liquid with a viscosity of 90 to 100 S.U.S.

ρ The test in the Vickers Plügel pump (20 hours, 52.7 kg / cm,

38 ^° C., 1200 rpm) resulted in a wear weight loss of 164 mg. Example 8

A water-based hydraulic fluid was prepared by mixing 1.9 % of the ester of polyoxyalkylated sorbitan monooleate available under the trademark "EMSORB 6905", 1.55 % of an emulsion (solids content 40%) of a sulfur-containing oxymolybdenum organophosphorodithioate and 0.4 % of the in Example 7 used phosphate ester. In addition, 14 % of the polyglycol thickener available under the trademark "PLURACOL V-IO" and 0.75 % of an isopropylaminoethanol mixture and 0.4 % sodium 2-mercaptobenzothiazole were used as corrosion protection and metal deactivators. The rest of the liquid was water. The hydraulic fluid was clear and amber in color and had a viscosity of 100 SUS at 38 ^° C.

ρ The test in the Vickers vane pump (20 hours, 52.7 kg / cm,

1200 rpm, 38 ^° C.) resulted in a wear weight loss of 211 mg. Example 9

A water-based hydraulic fluid was prepared according to Example 8, but without the use of the thickener. The liquid had a viscosity of less than 32 SUS at 38 ^° C., but still gave the good value of 242 g wear weight loss in the Vickers vane pump test under the same conditions as in Example 8.

Example 10 and 11

Two water-based hydraulic fluids were prepared containing one fifth of the same ingredients as the fluid of Example 8; one contained 14 % thickener,

- 25 809828/0764

- 25 - O.Z. 297O / OO899

the other was free of thickener. Both fluids were subjected to the test in the Vickers vane pump and brought good results. The thickened liquid, which has a viscosity of 100 S.U.S. at 38 ° C gave in 20 hours a weight loss of 289 mg, the non-thickened liquid in the same time 295 mg.

Examples 12-15

Examples 2 and 3 were repeated, but instead of the sulfur-containing molybdenum compound, a sulfur-containing oxyantimony organophosphorodithioate, which is available under the trademarks "VANLUBE 622" and "VANLUBE 6M8", was used. Hydraulic fluids with good properties were obtained.

Example 16

A hydraulic fluid concentrate with the following composition was produced:

Weight percent Polyoxyethylene 20 Sorbitan monostearate 38 Alkyl phosphate esters according to Example 5 8

Sulfur-containing oxymolybdenum organophosphorodithioate (40 % solids content) 31

Sodium-2-mercaptobenzothiazole 8 Isopropylaminoethanol 15

The clear, amber-colored, readily flowable concentrate showed no signs of phase separation after aging for 6 months at room temperature. The concentrate was diluted with tap water to form hydraulic fluids with a water content of 93.5 %, 95 %, 97 % and 99 % , which are homogeneous mixtures

- 26 - • 0 ** 28/07 * 4

- 26 - O.Z. 297O / OO899

acted. When testing in the Vickers vane pump under the In the conditions given in Example 1, these fluids gave wear weight losses of less than 250 mg.

BASF Wyandotte Corporation

809828/076 *

Claims (1)

Claim Hydraulic fluid or cutting fluid concentrate, which gives water lubricant properties, such as high pressure resistance and corrosion-inhibiting effect, characterized in that it (A) a water-soluble polyoxyethylated aliphatic ester, consisting of esters of ethoxylated aliphatic, one and polyhydric alcohols and ethoxylated aliphatic acids, the alcohols and acids mentioned having carbon chains have a length of 8 to 36 carbon atoms and the esters have been prepared by first at least polyoxyethylated one of the acids or one of the alcohols and then prepares the ester reaction product, and (b) a sulfur-containing metal compound of the formula in which M is molybdenum or antimony and R is the same or different Alkyl, aryl, alky lary Ires te nit 3 to 20 carbon atoms in the alkyl group mean contains. 80 «»? P / 07 * 4 ORIGINAL INSPECTED